Polyurethanes prepared from polyisocyanate, polyol and phosphonopolyester oligomers

ABSTRACT

Phosphonopolyester oligomers are prepared from hydroxyalkylated 2,2&#39;,-bis(3-allylphenyl-4-hydroxy) alkanes and phosphonyl dihalides. The oligomers are useful in the preparation of polyester resins, epoxy resins, and polyurethanes.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuaton, of application Ser. No. 330,106, filed Dec. 14,1981.

BACKGROUND OF THE INVENTION

The present invention concerns phosphonopolyester oligomers and reactionproducts thereof.

Phosphorus-containing materials are well known as fire retardant agentsin polymers such as polyester resins, polyurethane resins, epoxy resinsand the like, particularly when employed in combination with a halogensuch as chlorine or particularly bromine.

The present invention provides a method for incorporating phosphorusinto the polymer chain of such resins and in certain instances theoligomers of the present invention contain chlorine or bromine inaddition to phosphorus, in which instance a method for incorporatingboth phosphorus and a halogen into the polymer chain of the resins isprovided.

SUMMARY OF THE INVENTION

The present invention pertains to an oligomer having recurring unitsrepresented by the following general formula ##STR1## wherein each A isindependently --O--, --S--, --S--S--, ##STR2## or a divalent hydrocarbongroup having from 1 to about 8, preferably 1 to about 4, carbon atoms;each Q is independently oxygen or sulfur; each R is independently ahydrocarbon group having from about 1 to about 10, preferably from about1 to about 6, carbon atoms; each R' is independently a --CH═CH₂ group ora --CXH--CXH₂ group, wherein X is chlorine or bromine; each Z isindependently a terminal moiety; each m is independently zero or one;each m' independently has a value from 1 to about 5, preferably fromabout 1 to about 2; each n independently has a value of 2, 3 or 4; and xhas an average value of from 1 to about 10, preferably from 1 to about6.

The terminating moieties can be the same or different and are dependenton the ratio of the reactants employed to prepare the oligomer. When thephenolic hydroxyl-containing compound is in excess, most of the terminalmoieties are that which provides terminal hydroxyl groups and when thephosphonyl halide is employed in excess, most of the terminal moietiesare that which provides terminal phosphonate groups. Of course, it isrecognized that the composition is actually a mixture of oligomershaving various terminal moieties.

The present invention also pertains to polyurethanes, polyesters andepoxy resins prepared from the above oligomers.

DETAILED DESCRIPTION OF THE INVENTION

The oligomers of the present invention are prepared by reacting thedesired dihydroxyl-containing compound with the desired phosphonyldihalide or thiophosphonyl dihalide.

Suitable dihydroxyl-containing compounds which can be employed hereininclude those represented by the general formula ##STR3## wherein eachA, R', n, m and m' are as previously defined.

These compounds are readily prepared by alkoxylating with an appropriatealkylene oxide the allylated bisphenol compound or the brominatedallylated bisphenol compound.

The bisallylated bisphenols employed herein can be prepared by reactingthe appropriate bisphenol with an allyl halide in the presence of asuitable phase transfer catalyst such as DOWEX® MSA-1 ion exchangeresin, benzyltrimethyl ammonium halides, tetramethylammonium halides, ortetraalkylphosphonium halides, and an aqueous solution of an alkalimetal hydroxide such as NaOH at a temperature of from about 25° to about100° C. for from about 2 to about 24 hours. Thereafter, the pH isadjusted from about 7 to about 3 and the product, a bisallylatedbisphenol isomeric mixture, is recovered therefrom by separation of theoil and water phases. The resulting isomeric mixture is thermallyisomerized at about 200° C. for 1 to 2 hours to provide C-bisallylatedbisphenol. Mixtures of mono, di, and triallylated bisphenols are alsooperable.

Particularly suitable such compounds include, for example,dipropoxylated 2,2'-bis(3-allylphenyl-4-hydroxy) propane, diethoxylated2,2'-bis(3-allylphenyl-4-hydroxy) propane, dipropoxylatedbis(3-allylphenyl-4-hydroxy)methane, diethyoxylated or dipropoxylatedbisallylated 4,4'-dihydroxybiphenyl or 4,4'-dihydroxydiphenyl oxide or4,4'-thiodiphenol, and the like.

Suitable phosphonyl halides or thiophosphonyl halides which can beemployed herein include those represented by the general formula##STR4## wherein each Q, R, and X is as previously defined.

Unsaturated polyester resins can be prepared by reacting the oligomersof the present invention with polycarboxylic acids, anhydrides, ormixtures thereof. The oligomers may be employed alone as the sole sourceof hydroxyl groups or they can preferably be employed in combinationwith polyhydroxyl-containing materials such as aliphatic glycols.Suitable such polycarboxylic acids or anhydrides thereof andpolyhydroxyl-containing materials which can be employed to prepareunsaturated polyester resins as well as methods for such preparation andthe crosslinking and/or curing thereof can be found in KIRK OTHMERENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Vol. 20, pages 792-839, 1969, JohnWiley & Sons, Inc. which is incorporated herein by reference.

Particularly suitable polyesters are prepared by a hydrolysis methodwherein dicyclopentadiene or a dicyclopentadiene concentrate containingcyclopentadiene codimers and diolefin dimers is reacted with aα,β-unsaturated dicarboxylic acid anhydride and water to provide amixture consisting principally of dicyclopentadiene monomaleate andunreacted α,β-unsaturated dicarboxylic acid and anhydride. Alternately,the dicyclopentadiene and a α,β-unsaturated dicarboxylic acid may bereacted directly without water as a coreactant. The oligomer of thepresent invention plus a suitable glycol, polyol or mixture thereof isadded and polyesterification is completed by removal of water atelevated temperatures. Suitable hydrolysis methods are more fullydescribed in U.S. Pat. No. 4,148,765 and U.S. Pat. No. 4,233,432.

It is particularly desirable to perform the hydrolysis in a stagedmanner wherein the dicyclopentadiene or dicyclopentadiene concentrateand water are added in increments. This provides for additional controlover reaction exotherms. This method is more fully described in theaforementioned U.S. Pat. No. 4,148,765.

Epoxy resins can be prepared from the oligomers of the present inventionby reaction with an epihalohydrin in the presence of suitable acidcatalysts such as boron trifluoride etherate, stannic chloride, and thelike as described in HANDBOOK FOR EPOXY RESINS, by Lee and Neville,McGraw-Hill, 1967. The book also describes methods for curing epoxyresins such as with amines, polycarboxylic acids and anhydrides thereofand the like. The handbook by Lee and Neville is incorporated herein byreference.

Polyurethanes can be prepared from the oligomers of the presentinvention by reacting them with organic polyisocyanates in the presenceof suitable catalysts. The oligomers can be employed alone or incombination with other hydroxyl-containing materials. Suitablehydroxyl-containing materials, polyisocyanates, and catalysts, as wellas suitable methods for conducting the reaction, can be found inPOLYURETHANES: CHEMISTRY AND TECHNOLOGY II. TECHNOLOGY, by Saunders andFrisch, Interscience, 1964 which is incorporated herein by reference.

The following examples are illustrative of the invention but are not tobe construed as to limiting the scope thereof in any manner.

EXAMPLES 1-3

In a series of reactions, the bispropoxylate of2,2'-bis(3-allylphenyl-4-hydroxy)propane, 84.92 grams (0.20 mole), wascharged to a 3-necked round bottom reactor equipped with athermometer-temperature controller assembly and heating mantle. A drynitrogen inlet was fitted to the reactor and adjusted to maintainnitrogen flow over the surface of the reactants. Magnetic stirring wasemployed. A condenser and a side arm vented addition funnel containingphenylphosphonyl dichloride, 37.05 grams (0.19 mole), were added tocomplete the reactor. Heating commenced, and once the minimum reactiontemperature, as specified in Table I, was achieved, the phenylphosphonyldichloride was added dropwise over the specified time interval andtemperature range. A post reaction was then completed for the specifiedtime interval and temperature range. Finally, additional post reactionwas performed under vacuum of about 80 to 10 mm for the specified timeinterval and temperature range. At the end of the vacuum post reaction,the phosphonopolyester oligomer product was recovered as a light ambercolored solution which became an immobile gel at (25° C.) roomtemperature. The product was weighed and analyzed for average molecularweight by gel permeation chromatography. The results are reported inTable I.

COMPARATIVE EXPERIMENTS A-C

A series of comparative experiments were completed using the method ofExamples 1-3, with the following changes:

C.E. A

2,2'-bis(3-allylphenyl-4-hydroxy)-propane, 30.84 grams (0.10 mole), wassubstituted for the corresponding bispropoxylate of examples 1-3.Phenylphosphonyl dichloride was correspondingly reduced to 18.52 grams(0.095 mole) to maintain the stoichiometric ratio of examples 1-3. Theresults are reported in Table I.

C.E. B

The bispropoxylate of 4,4'-isopropylidenediphenol, 68.80 grams (0.20mole) was substituted for the 2,2'bis(3-allylphenyl-4-hydroxy)propane ofexamples 1-3. The results are reported in Table I.

C.E. C

2,2'-bis(3-allylphenyl-4-hydroxy)propane, 63.69 grams (0.15 mole) wasreacted with dichlorophenylphosphine, 25.51 grams (0.1425 mole). Theresults are reported in Table I.

                                      TABLE I                                     __________________________________________________________________________         Reaction Time (min.)                                                                      Reaction Temperature                                              (a) phosphorus dihalide                                                                   (°C.)                                                        addition  (a) initial-maximum                                                                       Average                                               (b) post reaction                                                                         (b) minimum-maximum                                                                       Molecular                                                                           Conversion.sup.3                           Example                                                                            (c) vacuum post reaction                                                                  (c) minimum-maximum                                                                       Weight.sup.1                                                                        (%)                                        __________________________________________________________________________    1    (a)   30                                                                              (a)     40-54   1282  82                                              (b)  119                                                                              (b)     74-102                                                        (c)  995                                                                              (c)     69-100                                                   2    (a)  30 (a)     40-50   2776  100                                             (b)  154                                                                              (b)     50-102                                                        (c)  1040                                                                             (c)     90-105                                                   3    (a)  30 (a)     39-60   2239  100                                             (b)  180                                                                              (b)     60-100                                                        (c)  1080                                                                             (c)     75-108                                                   C.E. A                                                                             (a)  30 (a)     38-63    253  --                                              (b)  120                                                                              (b)     68-110                                                        (c)  45.sup.2                                                                         (c)     101-110                                                  C.E. B                                                                             (a)  30 (a)     45-60    985  83                                              (b)  120                                                                              (b)     64-102                                                        (c)  960                                                                              (c)     99-107                                                   C.E. C                                                                             (a)  30 (a)     50-72    255  60                                              (b)  180                                                                              (b)     62-106                                                        (c)  60 (c)     100- 106                                                 __________________________________________________________________________     .sup.1 polystyrene standards                                                  .sup.2 reaction terminated  phenylphosphonyl dichloride distills overhead     during the vacuum post reaction.                                              .sup.3 based on weight of HCl lost.                                      

EXAMPLE 4

The bispropoxylate of 2,2'-bis(3-allylphenyl-4-hydroxy)propane, 63.69grams (0.15 mole), and phenylphosphonyl dichloride, 27.79 grams (0.1425mole), were reacted using the method of examples 1-3 except that 150grams of chloroform was used as a solvent for the reaction. Make-upchloroform was added as required to maintain a constant volume. Allchloroform was allowed to distill out of the reactor during the vacuumpost reaction. The following results were obtained:

Reaction time (min.)

(a) phosphorus dihalide addition--4

(b) post reaction--352

(c) vacuum post reaction--925

Reaction temperature (°C.)

(a) initial-maximum--50-54

(b) minimum-maximum--52-116

(c) minimum-maximum--100-120

Average Molecular Weight--1193

EXAMPLE 5

The bispropoxylate of 2,2'-bis(3-allylphenyl-4-hydroxy)-propane, 63.69grams (0.15 mole), and phenylphosphonyl dichloride, 29.25 grams (0.15mole), were reacted using the method of Examples 1-3. Exactlystoichiometric ratios of the aforementioned reactants are used in thisexample whereas less than stoichiometric phenylphosphonyl dichloride wasused in examples 1-4. The following results were obtained:

Reaction time (min.)

(a) phosphorus dihalide addition--20

(b) post reaction--130

(c) vacuum post reaction--78

Reaction temperature (°C.)

(a) initial-maximum--38-62

(b) minimum-maximum--60-102

(c) minimum-maximum--101-114

Average Molecular Weight--776

Conversion (%)--96

EXAMPLE 6

A phosphonopolyester oligomer product was synthesized using the methodand stoichiometry of examples 1-3. The average molecular weight was1136. This product was used as one of the components in the synthesis ofa dicyclopentadiene modified unsaturated polyester alkyd, as follows:

Maleic anhydride, 98.06 grams (1.0 mole), was charged to a reactor andmelted to a clear stirred solution maintained at 70° C. under a nitrogenatmosphere. Water, 9.46 grams (0.525 mole), was added followed by theaddition of an increment of dicyclopentadiene concentrate, 20.05 grams,two minutes later. The dicyclopentadiene concentrate contained 83.94%dicyclopentadiene, 14.41% codimers and dimers, 1.11% light hydrocarbons,and 0.55% cyclopentadiene. Twenty minutes later, additional incrementsof water, 3.15 grams (0.175 mole), and dicyclopentadiene concentrate,20.05 grams, were added. After 15 minutes additional dicyclopentadieneconcentrate, 20.05 grams, was added. A final increment ofdicyclopentadiene concentrate, 20.05 grams, was added 15 minutes laterand the temperature controller was set at 110° C. This temperature wasachieved 15 minutes later. Thirty minutes later, propylene glycol, 53.42grams (0.702 mole) and the phosphonopolyester oligomers, 88.58 grams(0.078 mole) were added and the steam condenser was started, nitrogensparging was increased, and the temperature controller was set at 160°C. This temperature was achieved 15 minutes later. After two hours ofreaction at 160° C., the temperature controller was set at 205° C. Thistemperature was achieved 35 minutes later. Reaction continued for 2.0hours at 205° C. during which time a total of 12 milliliters of waterlayer and 1.5 milliliters of organic material were removed through thesteam condensor and into the Dean Stark trap-cold water condenserassembly. The reactor was cooled to 170° C. and 100 ppm of hydroquinonewas added as an inhibitor. The polyester alkyd was recovered as a lightamber solid with a final acid number of 45.9.

The polyester alkyd (57.0 percent) was dissolved in styrene (43.0percent). The resulting formulation was used to determine Brookfieldviscosity (25° C.), SPI gel and cure times plus maximum exotherm, andBarcol hardness. Circular, clear, unfilled castings of 0.5 cm. thicknessand 3.5 cm. diameter were used in the evaluation of chemical resistanceto water and toluene. These castings were prepared using a cure systemof 1.0 percent methylethylketone peroxide and 0.3 percent VN-2accelerator and 0.01 percent dimethylaniline, followed by 2.0hours ofpost curing at 200° F. The following results were obtained:

Brookfield viscosity (cp)--1145

SPI Gel (84° C.)

gel time--3.8 min.

cure time--16.1 min.

max. exotherm--99 min.

Chemical Resistance Testing

(A) Water--7 days at 25° C.

initial Barcol hardness--46

final Barcol hardness--46

weight gain (%)--0.24

appearance--no change

(B) Toluene--7 days at 25° C.

initial Barcol hardness--48.7

final Barcol hardness--49.0

weight gain (%)--0.22

appearance--no change

EXAMPLE 7

A propoxylate of 2,2'-bis(3-allylphenyl-4-hydroxy)propane containing1.075 propylene oxide units per aromatic hydroxyl group was prepared.Using the methods of examples 1-3, 61.0 grams (0.1408 mole) of thepropoxylate was reacted with 24.71 grams (0.1267 mole) ofphenylphosphonyl dichloride using the following reaction conditions.

Reaction time (min.)

(a) phosphorus dihalide addition--1

(b) post reaction--85

(c) vacuum post reaction--108

Reaction temperature (°C.)

(a) initial-maximum--40-41

(b) minimum-maximum--41-100

(c) minimum-maximum--100-100

The phosphonopolyester oligomer product had an average molecular weightof 1876. Full conversion of phenylphosphonyl dichloride to product wasachieved.

EXAMPLE 8

The phosphonopolyester oligomer product of example 7 was used as one ofthe components in the synthesis of a dicyclopentadiene modifiedunsaturated polyester alkyd, as follows:

Maleic anhydride (196.12 grams, 2.0 moles) was charged to a reactor andmelted to a clear stirred solution maintained at 70° C. under a nitrogenatmosphere. Water (18.92 grams, 1.05 mole) was added followed by theaddition of an increment of dicyclopentadiene concentrate (39.79 grams,0.30 mole) two minutes later. A maximum exotherm of 113° C. resulted.The dicyclopentadiene concentrate contained 86.05% dicyclopentadiene,13.64% cyclopentadiene codimers and dimers, and 0.31% lighthydrocarbons. Twenty minutes later, additional increments of water (6.31grams, 0.35 mole) and dicyclopentadiene concentrate (39.79 grams, 0.30mole) were added. After fifteen minutes, additional dicyclopentadieneconcentrate (39.79 grams, 0.30 mole) was added. A final increment ofdicyclopentadiene concentrate (39.79 grams, 0.30 mole) was added fifteenminutes later and the temperature controller was set at 110° C. Thistemperature was achieved six minutes later. Thirty minutes later,propylene glycol (116.28 grams, 1.528 moles) and the phosphonopolyesteroligomer (60.0 grams, 0.032 mole) were added and the steam condenser wasstarted, nitrogen sparging was increased to 4 liters per minute, and thetemperature controller was set at 160° C. This temperature was achieved19 minutes later. After two hours at the 160° C. reaction temperature,the temperature controller was set at 205° C. This temperature wasachieved 16 minutes later. Reaction continued for 2.75 hours at 205° C.after which time a total of 49.0 milliliters of water layer and 2.5milliliters of organic material had been removed through the steamcondenser and into the Dean Stark trap-cold water condenser assembly.The reactor was cooled to 165° C. and 100 ppm of hydroquinone was addedas an inhibitor. The polyester alkyd was recovered as a pale yellowsolid with a final acid number of 29.7.

The polyester alkyd (171.0 grams) and styrene (129.0 grams) were mixedto form a 43.0% styrenated solution. The resulting solution was used todetermine SPI gel characteristics, Brookfield viscosity (25° C.), and aclear, unfilled casting was made for heat distortion temperature, Barcolhardness, tensile and flexural strength, and oxygen index testing.Oxygen index values were determined by ASTM D2863-76. A cure system of1.0% benzoyl peroxide and 0.01% dimethylaniline was used to cure thecasting at room temperature followed by post curing for 2.0 hours at 93°C. (200° F.). The following results were obtained:

Brookfield viscosity at 25° C.--190.5 cp

SPI Gel (84° C.)

gel time--2.6 min.

cure time--3.4 min.

maximum exotherm--214° C.

    ______________________________________                                        Heat Distortion Temperature                                                                       181° F.                                            Average Barcol Hardness                                                                           41.5                                                      Tensile Strength    4016 psi (282.3 kg/cm.sup.2)                              Elongation          0.99%                                                     Flexural Strength   9773 psi (687 kg/cm.sup.2)                                Flexural Modulus    4.98 × 10.sup.-5 psi                                                    (3.5 × 10.sup.-6 kg/cm.sup.2)                       Oxygen Index        atmospheric                                               ______________________________________                                    

EXAMPLE 9

A portion of the polyester alkyd (253.0 grams) of example 8 wasdissolved in 1200 milliliters of methylene chloride then chilled to -20°C. and held under a nitrogen atmosphere. Bromine (78.33 grams) was addedover a 41 minute period followed by 60 minutes of post reaction at the-20° C. temperature. An inhibitor-stabilizer package consisting of 0.2%t-butyl catechol, 1.0% styrene, and 2.0% of the diglycidyl ether of apolyglycol (sold commercially as D.E.R.® 736 epoxy resin) having anepoxy equivalent weight of 175-205 was added and the solution wasallowed to warm to 25° C. The methylene chloride solvent was removedunder reduced pressure and styrene (190.86 grams) was added to form a43.0% styrenated solution. The physical and mechanical properties ofthis formulation were determined using the method of example 8. Thefollowing results were obtained:

Brookfield viscosity at 25° C.--482 cp

SPI Gel (84° C.)

gel time--3.15 min.

cure time--4.45 min.

maximum exotherm--145.5° C.

    ______________________________________                                        Heat Distortion Temperature                                                                       116° F.                                            Average Barcol Hardness                                                                           30.0                                                      Tensile Strength    4626 psi (536.1 kg/cm.sup.2)                              Elongation          1.55%                                                     Flexural Strength   11,264 psi (791.9 kg/cm.sup.2)                            Flexural Modulus    12.76 × 10.sup.-5 psi                                                   (8.97 × 10.sup.-6 kg/cm.sup.2)                      Oxygen Index        28.2                                                      ______________________________________                                    

COMPARATIVE EXPERIMENT D

A comparative dicyclopentadiene modified unsaturated polyester wasprepared as follows:

A hydrolysis step was completed in identical manner to example 8, After30 minutes at the 110° C. reaction temperature, propylene glycol (118.72grams, 1.56 moles) was added to the reactor and the steam condenser wasstarted, nitrogen sparging was increased to 4 liters per minute, and thetemperature controller was set at 160° C. The 160° C. temperature wasreached 16 minutes later. After 2 hours at 160° C., the temperaturecontroller was set at 205° C. and this temperature was achieved 20minutes later. After 2.3 hours a total of 41.5 milliliters of waterlayer and 11.0 milliliters of organic material were collected in theDean Stark trap. The reactor was cooled to 164° C. and 100 ppm ofhydroquinone was added. The polyester alkyd was recovered as a lightyellow solid with a final acid number of 34.7.

A 43.0% styrene-57.0% alkyd solution was prepared and used to determinethe following physical properties:

Brookfield viscosity at 25° C.--60.5 cp

SPI Gel (84° C.) P1 gel time--3.4 min.

cure time--4.8 min.

maximum exotherm--195° C.

    ______________________________________                                        Heat Distortion Temperature                                                                       231° F.                                            Average Barcol Hardness                                                                           47.7                                                      Tensile Strength    3113 psi (218.8 kg/cm.sup.2)                              Elongation          0.71%                                                     Flexural Strength   9951 psi (699.6 kg/cm.sup.2)                              Flexural Modulus    5.36 × 10.sup.-5 psi                                                    (3.77 × 10.sup.-6 kg/cm.sup.2)                      Oxygen Index        atmospheric                                               ______________________________________                                    

EXAMPLE 10

A phosphonopolyester oligomer was prepared from the bispropoxylate of2,2'bis(3-allylphenyl-4-hydroxy)propane and phenylphosphonyl dichlorideusing the methods and stoichiometry of examples 1-3. The averagemolecular weight was 1193. A portion of the oligomer, 30.0 grams (0.0252mole) was dissolved in 1,4-dioxane, 100 grams, containingdiphenylmethane-4,4'-diisocyanate, 3.30 grams (0.0277 mole). Thesolution was maintained at reflux (102°-104° C.) for 2.0 hours. Afterremoval of the solvent, a thermoplastic phosphonopolyesterurethane withhigh surface gloss, was recovered. The average molecular weight was5199.

EXAMPLE 11

A phosphonopolyester oligomer was prepared fom the bispropoxylate of2,2'-bis(3-allylphenyl-4-hydroxy)propane and phenylphosphonyl dichlorideusing the methods and stoichiometry of Examples 1-3. The averagemolecular weight was 1282. A portion of the oligomer, 50.0 grams (0.0390mole) and dipropylene glycol, 5.233 grams (0.0390 mole) were dissolvedin 1,4-dioxane, 100 grams, containing diphenylmethane-4,4'-diisocyanate,20.42 grams (0.0858 mole). The solution was maintained at reflux(106°-112° C.) for 2.0 hours. After removal of the solvent athermoplastic phosphonopolyesterurethane with high surface gloss wasrecovered. The average molecular weight was 4581.

I claim:
 1. A polyurethane prepared by reacting in the presence of asuitable catalyst system a composition comprising(A) an organic compoundcontaining a plurality of --NCO or --NCS groups; with (B) a mixtureof(1) a polyol containing from about 2 to about 8 active hydrogen groupsper molecule and an average active hydrogen equivalent weight of fromabout 30 to about 3000; and (2) an oligomer or mixture of oligomerscontaining hydroxyl groups having recurring units represented by thefollowing general formula ##STR5## wherein each A is independently--O--, --S--, --S--S--, ##STR6## or a divalent hydrocarbon group havingfrom 1 to about 8 carbon atoms; each Q is independently oxygen orsulfur; each R is independently a hydrocarbon group having from about 1to about 10 carbon atoms; each R' is independently a --CH═CH₂ group or a--CXH--CXH₂ group, wherein X is chlorine or bromine; each Z isindependently a terminal moiety; each m is independently zero or one;each m' independently has a value from 1 to about 5; each nindependently has a value of 2, 3 or 4; and x has an average value offrom 1 to about 10; and wherein components (1) and (2) are present inquantities such that from about 0 to about 95 percent of the activehydrogen atoms are contributed by component (1) and from about 5 toabout 100 of the active hydrogen atoms are contributed by component (2)and wherein components (A) and (B) are present in quantities such thatthe ratio of --NCO and/or --NCS groups to active hydrogen groups is fromabout 0.85:1 to about 4:1.
 2. A polyurethane of claim 1 wherein inComponent 2, each A is independently a divalent hydrocarbon group havingfrom 1 to about 4 carbon atoms; Q is oxygen; each R is independently ahydrocarbon group having from about 1 to about 6 carbon atoms; each mhas a value of 1, each m' independently has a value of from about 1 toabout 2; each n has a value of 3; and x has an average value of fromabout 1 to about
 10. 3. A polyurethane of claim 2 wherein in Component2, each A independently is a divalent hydrocarbon group having either 1or 3 carbon atoms; each m' has a value of 1; and n has a value of
 3. 4.A polyurethane of claim 1, 2 or 3 wherein component (A) contains only--NCO groups and the ratio of --NCO groups to active hydrogen groups isfrom about 0.95 to about 1.25.